CN110785448A

CN110785448A - Polymers suitable as thickeners

Info

Publication number: CN110785448A
Application number: CN201880038623.4A
Authority: CN
Inventors: D·伯纳特; R·纳吉尔斯迪克; A·L·斯坦梅茨; J·亚当斯; G·M·泽迪; W·A·胡夫; D·莱特费尔德
Original assignee: Bick American Co; BYK Chemie GmbH
Current assignee: BYK Chemie GmbH
Priority date: 2017-04-13
Filing date: 2018-04-12
Publication date: 2020-02-11
Also published as: US11377553B2; US20210115183A1; US11370912B2; CN110785447B; JP2020516733A; EP3609941B1; JP6995878B2; WO2018189294A1; EP3609940A1; WO2018189297A1; JP2020516732A; CN110785447A; EP3609941A1; EP3609940B1; JP6899003B2; US20200377723A1

Abstract

The invention relates to a polymer R comprising structural units according to formula (I) ¹‑X‑(C＝O)‑NH‑R ²‑NH‑(C＝O)‑O‑POA‑R ³‑(O‑POA‑R ⁴) _nWherein R is ¹The representatives have 6 to 50A hydrocarbon-terminated organic radical of carbon atoms, X representing O or N-R ⁵Wherein R is ⁵Represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, R ²Represents an aliphatic hydrocarbon group having 4 to 40 carbon atoms, POA represents a polyoxyalkylene group, R ³Represents an organic group having 2 to 40 carbon atoms, n is an integer of 1 to 6, R ⁴Independently selected from: - (C ═ O) -NH-R ²‑NH‑(C＝O)‑X‑R ¹、‑(C＝O)‑NH‑R ¹、‑R ⁶Wherein R is ⁶Represents a hydrogen atom or an aliphatic or aromatic group having from 1 to 24 carbon atoms and wherein the polymer has an average of at least 1.8 terminal groups R per molecule ¹A number average molecular weight of 2000 to 100000 daltons, a polydispersity of 1.0 to 5.0, wherein the quotient of the polydispersity divided by (n +1) is less than 1.0, with the proviso that the polymer is not the reaction product of a) a mono-adduct of isophorone diisocyanate and 1-dodecanol with b) a polyether based on glycerol and a mixture of ethylene oxide and propylene oxide having an OH value of 18mg KOH/g.

Description

Polymers suitable as thickeners

The present invention relates to a modified urethane polymer, a process for preparing said polymer, the use of said polymer as a thickener in aqueous liquid compositions, and compositions comprising said polymer and a continuous aqueous liquid phase.

Hydrophobically modified ethoxylated urethanes, abbreviated as HEUR, and their use as thickeners are known in the art. HEUR thickeners are typically prepared in a random polymerization process in which a diisocyanate is reacted with polyethylene glycol and optionally a branching agent and a hydrophobic monoalcohol to terminate the polymer chain. Such a process is described in US 4,079,028. The random nature of the reaction of the isocyanate with the polyol produces polymers with broad molecular weight distributions.

It has been found that the known HEUR thickeners, when used in aqueous coating compositions, produce coating compositions which are not completely satisfactory in terms of substrate wetting, hiding properties and flow properties.

The present invention seeks to provide thickeners which alleviate or eliminate the above disadvantages.

It should be noted that US 4,794,147 describes the reaction of 2, 4-toluene diisocyanate and methyl-terminated polyethylene glycol under mild conditions to produce predominantly a mono-adduct at the 4-position. The mono-adduct is then reacted with diethanolamine to produce a diol that can be incorporated into a urethane coating resin to provide in situ nonionic stabilization.

US 5,175,22 describes the reaction product of isophorone diisocyanate and branched polyalkylene oxides to prepare self-crosslinking gels for biomedical use. In this case, the inventors used 1 mole of diisocyanate to 1 mole of hydroxyl functionality. The resulting polymer gels the aqueous system by reaction with water.

The invention provides a polymer comprising structural units according to formula (I),

R ¹-X-(C＝O)-NH-R ²-NH-(C＝O)-O-POA-R ³-(O-POA-R ⁴) _n(I)

wherein

R ¹Independently selected from organic groups terminated with hydrocarbon groups having from 6 to 50 carbon atoms,

x is independently selected from O or NR ⁵Wherein R is ⁵Represents a hydrogen atom or an aliphatic or aromatic group having 1 to 30 carbon atoms,

R ²independently selected from aliphatic hydrocarbon groups having 4 to 40 carbon atoms,

POA represents a polyoxyalkylene group

R ³Independently selected from organic groups having 2 to 12 carbon atoms,

n is an integer of 1 to 6

R ⁴Is independently selected from

-(C＝O)-NH-R ²-NH-(C＝O)-X-R ¹、

-(C＝O)-NH-R ¹、

-R ⁶Wherein R is ⁶Represents a hydrogen atom or an aliphatic or aromatic group having 1 to 24 carbon atoms,

and wherein the polymer has an average of at least 1.8 end groups R per molecule ¹A number average molecular weight of 2000 to 100,000 daltons, a polydispersity of 1.0 to 5.0, and wherein the quotient of the polydispersity divided by (n +1) is less than 1.0, with the proviso that the polymer is not the reaction product of a) a mono-adduct of isophorone diisocyanate and 1-dodecanol with b) a polyether based on glycerol and a mixture of ethylene oxide and propylene oxide having an OH value of 18mg KOH/g.

It should be noted that the term mono-adduct of isophorone diisocyanate refers to a compound in which one isocyanate group of isophorone diisocyanate has been reacted with 1-dodecanol while the other isocyanate group has not reacted.

In a preferred embodiment, the polymer has a content of structural units according to formula (I) of at least 70 wt. -%, based on the total mass of the polymer.

The polymers of the invention can be used very advantageously as thickeners, especially in aqueous liquid compositions, for example in aqueous coating compositions. When used as a thickener in an aqueous coating composition, the polymers of the present invention result in coating compositions that exhibit improvements in substrate wetting, hiding properties, and flow properties.

Associative thickeners are usually supplied as aqueous solutions with a thickener content of 15 to 25% by weight. The solution preferably contains a higher thickener content and lower water content, since the lower water content in the additive results in a higher formulation latitude in the thickened product (e.g., paint). Many thickeners using the polymers of the present invention can be dissolved at higher concentrations without the use of viscosity inhibiting materials. Such inhibitors are preferably avoided as they may affect the properties of the final product.

It should be noted that the various groups in the polymer according to formula (I) as defined above may be selected independently of each other. If the polymer comprises two or more groups of the same definition, these groups are likewise independently selected as long as they fall within the definitions provided for the groups.

R ¹Represents an organic group terminated with a hydrocarbon group having 6 to 50 carbon atoms. The hydrocarbyl group may be aliphatic, aromatic or alkyl aromatic. The hydrocarbyl group may be branched or unbranched and may be saturated or unsaturated. Examples of suitable hydrocarbyl groups include branched or linear alkyl groups having from 7 to 30 carbon atoms, particularly from 8 to 22 carbon atoms. Preferred alkyl groups include linear and branched alkyl groups having from 8 to 18 carbon atoms; in one embodiment, branched alkyl groups are preferred. Another suitable hydrocarbon group is tristyrylphenyl, especially 2,4, 6-tris (1-phenylethyl) phenyl.

In one embodiment, R ¹Consisting of a terminal hydrocarbon group as defined above. In this case, at least one R ¹Represents a hydrocarbon group having 6 to 30 carbon atoms. If the polymer contains more than one R ¹Then each R ¹May be the same or different. In a further embodiment, R ¹Represents a polyoxyalkylene group terminated by a hydrocarbon group as defined above. Examples of suitable types of polyoxyalkylene groups include polymers of ethylene oxide, propylene oxide and butylene oxide. In addition to polymers based on these and other monofunctional epoxides, polymers based on oxetane and tetrahydrofuran, and copolymers and block copolymers thereof may also be used. In still further embodiments, R ¹Represents a polyester group terminated by a hydrocarbon group having 6 to 30 carbon atoms. Specific examples of suitable polyester groups include polymers and oligomers obtained by ring-opening polymerization of epsilon caprolactone and gamma butyrolactone. In the further implementationIn the embodiment, R ¹Comprising a combination of polyether and polyester segments, for example polyether and polyester blocks, and terminated by a hydrocarbon group as defined above. In a preferred embodiment, R ¹Represents a polyoxyalkylene group composed of ethylene oxide and propylene oxide based units capped with a hydrocarbon group having 8 to 30 carbon atoms. In a very preferred embodiment, R ¹Represents a polyethylene oxide group terminated with an alkyl group having 8 to 18 carbon atoms or with a tristyrylphenyl group.

In a preferred embodiment, X in formula (I) represents an oxygen atom. Or X represents N-R ⁵Group, wherein R ⁵Represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbyl group may be branched or unbranched and may be saturated or unsaturated. Examples of suitable hydrocarbyl groups include branched or linear alkyl groups having 1 to 10 carbon atoms, for example lower alkyl groups having 1 to 6 carbon atoms.

R in formula 1 ²Represents an aliphatic hydrocarbon group having 4 to 40 carbon atoms. Aliphatic hydrocarbon radical R ²May be linear or branched, or cycloaliphatic. Specifically suitable R ²Examples of radicals are the following structures, where the asterisks indicate R ²Position of attachment to the rest of the molecule:

POA in the formula (I) represents a polyoxyalkylene group. Examples of suitable types of polyoxyalkylene groups include polymers of ethylene oxide, propylene oxide and butylene oxide. In addition to epoxide-based polymers, polymers based on oxetane and tetrahydrofuran, and copolymers and block copolymers thereof may also be used. In a preferred embodiment, the polyoxyalkylene group comprises units- [ C ] selected from ethylene oxide-based units ₂H ₄-O]And units based on propylene oxide- [ C ₃H ₆-O]-a repeating unit of (a).

It is particularly preferred that the amount of repeating units based on ethylene oxide is higher than 65% by weight, preferably higher than 75% by weight, relative to the total amount of repeating units based on ethylene oxide and propylene oxide. In one embodiment, the polyoxyalkylene groups are solely ethylene oxide based repeating units.

The polyoxyalkylene groups specified by the POA typically together contain at least a total of 50 ether oxygen atoms, preferably at least 100 or 130 ether oxygen atoms, more preferably at least 150 ether oxygen atoms. The polyoxyalkylene groups specified by POA generally together contain up to a total of 1500 ether oxygen atoms, preferably up to 1200, more preferably up to 1000.

R in the formula (I) ³Represents an organic group having 2 to 40 carbon atoms. In many embodiments where the polymer of the present invention is a substantially linear unbranched polymer, R ³Is an alkylene group having 2 to 4 carbon atoms, such as ethylene or propylene. In other embodiments, the polyoxyalkylene groups may be branched. In this case R ³Represents a hydrocarbon residue of a polyfunctional alcohol such as glycerol, trimethylolpropane, pentaerythritol, ditrimethylolpropane or dipentaerythritol. However, R ³Other groups, such as groups derived from polyisocyanates, may also be included.

N in formula (I) represents an integer of 1 to 6. If n is 1, the polymer is a linear polymer. In some embodiments, the polymers of the present invention are preferably substantially linear. For specific applications, branched polymers may be beneficial. In some embodiments, the polymer contains a mixture of structures with different degrees of branching, for example, there is a mixture of molecules where n is 1, 2, and 3.

R in the formula (I) ⁴Is independently selected from

-(C＝O)-NH-R ²-NH-(C＝O)-X-R ¹、

-(C＝O)-NH-R ¹、

-R ⁶Wherein R is ⁶Represents a hydrogen atom or an aliphatic or aromatic group having 1 to 24 carbon atoms.

At R ⁴Is- (C ═ O) -NH-R ²-NH-(C＝O)-X-R ¹In embodiments of (a) the structure of the end group is similar to the junction defined above for the other ends of the polymerAnd (5) forming. In some cases, this embodiment is preferred.

In other embodiments, R ⁴Represents- (C ═ O) -NH-R ¹. The structure can be described as a hydroxyl terminated polyoxyalkylene group with the formula R ¹Reaction products of isocyanates of NCO.

In still further embodiments, R ⁴represents-R ⁶Wherein R is ⁶Represents a hydrogen atom or an aliphatic or aromatic group having 1 to 24 carbon atoms. When R is ⁶When hydrogen, the structure can be described as a hydroxyl group terminating a polyoxyalkylene group. When R is ⁶When an aliphatic or aromatic group having 1 to 24 carbon atoms, the structure can be described as an ether group terminating a polyoxyalkylene group. In some embodiments, R ⁶Is an aliphatic group having 1 to 5 carbon atoms. Suitable examples of aliphatic groups include lower alkyl groups such as methyl, ethyl and propyl and butyl. In a further embodiment, R ⁶And may be a lipophilic hydrocarbon group having 6 to 18 carbon atoms.

According to formula (I), each polymer molecule may comprise at least 1 terminal group R ¹And n is 6 and all R ⁴The group comprising R ¹In an embodiment of the radicals, up to 7 terminal groups R ¹. Typically, the polymers are made from polymers that may have different R' s ¹A mixture of different independent molecules of the number of end groups. Average R of the polymer ¹The number of end groups is defined as R ¹The total number of end groups divided by the number of polymer molecules. According to the invention, the polymer has an average of at least 1.8 end groups R ¹. Typically, the polymer has 1.8 to 4.0 terminal groups R ¹. In embodiments where the polymer is a linear polymer, the terminal group R ¹The number is suitably in the range 1.8 to 2.0.

The polymer has a number average molecular weight of 2000 to 100000 daltons. In a preferred embodiment, the number average molecular weight is 8000- & lt 50,000.

The molecular weight can be suitably determined by Gel Permeation Chromatography (GPC) using polyethylene glycol as a calibration standard and THF as the eluent.

Furthermore, the polymers according to the invention preferably have a content of structural units according to formula (I) of at least 80 wt.%, calculated on the total mass of the polymer.

Polydispersity is defined as the mass average molecular weight Mw divided by the number average molecular weight Mn. Both Mn and Mw can be determined by GPC as described above.

The polydispersity is generally preferably low, for example in the range from 1.0 to 5.0. Preferably, the polydispersity does not exceed 4.0, more preferably 2.5, 2.2 or even 2.0.

The invention also relates to polymers according to formula (I) wherein the quotient of the polydispersity divided by (n +1) is preferably less than 0.9 or 0.8. For such quotient, n represents the integer n in formula (I).

The polymeric or oligomeric starting materials used to prepare the polymers of the present invention already have a molecular weight distribution and polydispersity.

In particular, the polymer according to formula (I) comprises polyoxyalkylene groups. In certain embodiments, the raw materials comprising polyoxyalkylene groups already have a relatively high polydispersity. Thus, the polydispersity of the polymer made from such raw materials may also exceed 5.0. If so, the content of structural units according to formula (I) should be at least 70% by weight, calculated on the total mass of the polymer. In some embodiments, the content of structural units according to formula (I) is at least 90 wt. -%, or even 95 wt. -% or 100 wt. -%, based on the total mass of the polymer.

In a preferred embodiment, the polymers of the invention have a polydispersity of from 1.0 to 5.0 and a content of structural units according to formula (I) of at least 70% by weight, calculated on the total mass of the polymer.

The invention also relates to a method for producing a polymer according to formula (I). The process comprises reacting an isocyanate compound of formula (II)

R ¹-X-(C＝O)-NH-R ²-NCO(II)

With a hydroxy-functional polyoxyalkylene group-containing compound of the formula (III)

HO-POA-R ³-(O-POA-R ⁴) _n(III)

Wherein R is ¹To R ⁴POA, X and n are as explained above.

In a preferred embodiment, at least one R in the formula (III) ⁴The radicals are hydrogen atoms. More preferably, all R in formula (III) ⁴The radicals are hydrogen atoms.

Optionally, it is possible to include additional R ⁷-(NCO) _mOf (a) in which R is ⁷Represents an organic group having 1 to 40 carbon atoms and m is an integer of 1 to 10.

The reaction of the compounds of formula (II) and (III) is suitably carried out at a temperature in the range 20 to 120 ℃, although temperatures outside this range are also possible if desired. The preferred temperature range is from 50 to 100 ℃ and in particular from 60 to 90 ℃. If desired, the reaction may be carried out in the presence of a catalyst for catalyzing the reaction between isocyanate groups and hydroxyl groups. Such catalysts are well known in the art. The process can be carried out in the absence or presence of a solvent. In some embodiments, it is preferred to carry out the process in the absence of a solvent. The process can be carried out as a batch process or as a semibatch process.

In one embodiment, the process is carried out in a continuous mode, wherein the compounds of formula (II) and (III) are continuously fed to and passed through a reaction zone, and wherein the polymer of formula (I) is continuously withdrawn from the reaction zone. The compounds of formulae (II) and (III) may be fed to the reaction zone independently or as a premix. Suitable apparatus for the continuous process include extruders or kneaders, for example twin-screw extruders, such as machines such as CRP-63 or CRP-630 from LIST AG of Basel, Switzerland.

In a typical embodiment of the process, the reaction is carried out by reacting a compound of the formula OCN-R ²Diisocyanates of the formula-NCO (IV) & formula R ¹Reaction of a compound of formula XH (V) to obtain a compound of formula (II). Suitable diisocyanates are based on the hydrocarbon radicals R mentioned above ²Those of (a). Formula R ¹Examples of the compound of-XH (V) include alcohols (X is oxygen) and amines (X is N-R) ⁵). Specific examples of the compound of formula (V) include fatty alcohol ethoxylates terminated with hydroxyl groups.

The reaction of the diisocyanate of formula (IV) with the compound of formula (V) preferably selectively provides the monoadduct of formula (II). The content of the di-adduct in which both isocyanate groups have reacted with the compound of formula (V) and the content of unreacted diisocyanate are preferably low. Typically, the reaction product contains at least 80 mole% of the compound of formula (II), preferably at least 90 mole% or even up to 95 or 99 mole% or more. In order to achieve a high content of mono-adducts, it is preferred that the reactivity of the isocyanate groups of the diisocyanates of the formula (IV) with the compounds of the formula (V) is different. Examples of preferred diisocyanates have the formula:

with such highly selective diisocyanates, it is possible to achieve monoadducts even with low or no molar excess of diisocyanate relative to the compound of formula (V). A molar excess of diisocyanate may likewise be used. Generally, a molar excess of diisocyanate relative to the compound of formula (V) increases the yield of the monoadduct. The molar ratio of the compound of formula (V) to the diisocyanate is generally from 1:8 to 1:1, preferably from 1:4 to 1:1, more preferably from 1:2.5 to 1: 1. In embodiments where a molar excess of diisocyanate is used in the reaction, the excess diisocyanate is suitably removed after the reaction is complete, for example by distillation.

The high content of the monoadduct of formula (II) and the low content of the diadduct and unreacted diisocyanate results in a polymer of formula (I) having the desired low polydispersity or a low increase in the polydispersity of the polymer compared to the polydispersity of the polyoxyalkylene group containing starting material. Generally, the polydispersity of the polymer of formula (I) is 0 to 15% higher, preferably 0 to 10% higher, than the polydispersity of the raw material comprising polyoxyalkylene groups.

When it is prepared in a process in which the amount of isocyanate having two or more isocyanate groups used in the reaction does not exceed 30% by weight, calculated on the total amount of isocyanate-functional starting materials used in the process, it is possible to obtain a polymer which meets the requirements described above, and in which the content of structural units according to formula (I) is at least 70% by weight, calculated on the total mass of the polymer. It is generally preferred that the amount of isocyanate having two or more isocyanate groups is as low as possible, for example at most 20 wt% or at most 10 wt% or at most 5 wt% calculated on the total amount of isocyanate-functional starting materials used in the process.

The polymers of the invention can be very advantageously used as thickeners in liquid aqueous compositions.

Aqueous compositions are those in which the main or only liquid diluent used is water. Preferably, the aqueous system contains less than 35 wt. -%, 25 wt. -%, 20 wt. -% or even less than 10 wt. -% of (volatile) organic solvent based on the total weight of water and organic solvent in the liquid formulation. In some embodiments, the aqueous system is free of organic solvents. The aqueous system may contain water-soluble organic or inorganic compounds, for example ionic compounds such as salts.

The use generally comprises adding the polymer to an aqueous liquid composition and increasing/controlling the viscosity of the aqueous liquid composition. Examples of suitable aqueous liquid compositions include coating compositions, (pre) polymer compositions, pigment concentrates, ceramic products, sealants, cosmetic formulations, adhesives, casting compounds, lubricants, inks, cleaners, liquids for oil and gas extraction, putties, metal working fluids, sprayable fluids such as deposition aids for crop protection, wax emulsions, liquids for energy storage media such as batteries, liquids for electrical or electronic components, casting or potting compositions and building materials.

The invention also relates to a composition comprising

a) The continuous aqueous liquid phase is a continuous aqueous liquid phase,

b) a polymer according to formula (I) dissolved in a continuous aqueous liquid phase, and

c) a hydrophobic component dispersed in the continuous aqueous liquid phase.

The continuous aqueous liquid phase contains water and is liquid at a temperature of 20 ℃. The hydrophobic component may be an organic component, for example an organic compound or an organic polymer, such as a film-forming binder. Alternatively, the hydrophobic component may be an inorganic component having hydrophobic properties. In some embodiments, different organic and/or inorganic component combinations are present as component (c) of the composition.

In a highly preferred embodiment, the hydrophobic component is a film-forming polymeric binder.

In one embodiment, the composition further comprises solid particles. Examples of solid particles include pigments, fillers, and combinations thereof. The composition may contain other ingredients and additives commonly used in aqueous compositions, such as organic cosolvents, crosslinking agents, antifoaming agents, dispersing aids, and uv stabilizers. Although the polymers according to the invention provide excellent thickening properties, it is possible to use the polymers of the invention in combination with other rheology control agents, if desired.

Examples of other rheology control agents include clay-based thickeners, polysaccharides (e.g. cellulose derivatives, guar gum, xanthan gum), urea compounds, (poly) amides, polyacrylates (e.g. alkali soluble or swellable emulsions) or associative thickeners (e.g. polyurethane thickeners, aminoplast-based thickeners, hydrophobically modified alkali soluble emulsion thickeners).

In a particular example, the polymers of the present invention may be used in combination with other associative thickeners that affect the low, medium and/or high shear properties of the liquid aqueous composition whose rheological behavior needs to be modified.

Typically, the polymer of the present invention is present in the aqueous liquid composition in an amount of at least 0.1 wt.%, such as 0.2 or 0.3 wt.%, or preferably at least 0.5 wt.%, calculated on the total weight of the composition.

Typically, the polymer of the present invention is present in the aqueous liquid composition in an amount of up to 7.0 wt.%, such as 5.0 or 4.0 wt.%, or preferably up to 3.0 wt.%, calculated on the total weight of the composition.

Aqueous compositions as coating compositions or inks can be used in various fields of application, such as automotive coatings, architectural coatings, protective coatings (e.g. marine or bridge coatings), can and coil coatings, wood and furniture coatings, industrial coatings, plastic coatings, wire enamels, food and seed coatings, leather coatings (for natural and artificial leathers), color photoresists (e.g. for LC displays). The coating material includes a paste-like material generally having a high solid content and a low liquid component content, such as a pigment paste or effect pigment paste (using pigments based on aluminum, silver, brass, zinc, copper, bronze such as gold bronze, iron oxide-aluminum); further examples of effect pigments are interference pigments and pearlescent pigments, such as metal oxide-mica pigments, bismuth oxychloride or basic lead carbonate.

The (pre) polymer compositions mentioned are aqueous liquid raw materials for the manufacture of plastic compounds, which are preferably cured by chemical crosslinking.

The cosmetic composition may be all kinds of aqueous liquid compositions for personal care or health care use. Examples are lotions (lotions), creams, ointments such as toothpaste, foams such as shaving foam, gels such as shaving gel and bath gel, pharmaceutical compounds in gel-like administration forms, shampoos, liquid soaps, nail varnishes, lipsticks and hair dyes.

The preferred wax emulsion is an aqueous dispersion of wax particles formed from a wax that is solid at room temperature.

Sprays, preferably for use as deposition aids, may be formulated with the polymers of the invention to achieve drift (drift) mitigation. They may, for example, contain fertilizers or herbicides, fungicides and other pesticides.

Formulations for construction purposes may be materials that are liquid or pasty during handling and processing; these aqueous materials are used in the construction industry and they become solid after a setting time, for example hydraulic binders, such as concrete, cement, mortar/mortar, tile adhesives and gypsum.

Metalworking fluids are aqueous compositions used to treat metals and metal parts. Examples are cutting fluids, drilling fluids (for drilling of metals), release agents (mostly aqueous emulsions, for example in aluminium die casting and foundry applications), foundry washes (foundry washes), foundry paints, and liquids for surface treatment of metals, such as surface finishing, surface cleaning and electroplating.

Lubricants are aqueous compounds for lubricating applications, i.e. for reducing wear and friction losses, or for improving cooling, force transmission, vibration damping, sealing effect and corrosion protection.

The liquid formulation for oil and gas production is an aqueous formulation for opening and producing a reservoir. An aqueous drilling fluid or "drilling mud" is a preferred example. One application example is hydraulic fracturing.

The cleaning agent can be used for cleaning different kinds of objects. They help remove contaminants, residual dirt and adhering debris. Cleaning agents also include detergents (especially for cleaning fabrics, their precursors and leather), detergents (clearers) and polishes, laundry formulations, fabric softeners and personal care products.

The adhesive may be all kinds of aqueous materials that are liquid under processing conditions and can join adhered parts by promoting surface adhesion and internal strength.

The polymers of the present invention may be provided as solid additive materials (e.g., as flakes, pellets, granules). In this case, it is very much preferred that at least 70%, 80%, 95% or even 100% by weight of the solid material consists of the polymer of formula (I) according to the invention.

Alternatively, the polymer may be provided as an aqueous additive composition.

The invention also relates to an additive composition comprising

a)10.0 to 60.0% by weight of a polymer according to the invention,

b)40.0 to 90.0 wt.% of water,

c)0.0 to 1.0% by weight of a biocide, and

d)0.0 to 75.0 wt% of a viscosity inhibitor.

The wt. -% relates to the relative ratios of components a) to d) in the additive composition.

Examples of suitable viscosity inhibitors include polyalkylene oxides, especially those based on ethylene oxide, propylene oxide and mixtures thereof, butyl diglycol, cyclodextrins and alkyl polyglycosides. Further examples of viscosity inhibitors are described in US 2007/161745.

Viscosity inhibitors are optional components of the additive composition of the present invention. If present, the additive composition generally comprises up to 75.0% by weight, calculated on the sum of components a) to d), of a viscosity inhibitor, preferably up to 60.0 or 55.0% by weight. In some embodiments, the amount of viscosity inhibitor may be less than 10.0 wt.%, for example 2.0 to 4.0 wt.%, calculated on the sum of components a) to d). In yet another embodiment, no viscosity inhibitor is used at all.

Examples

Preparation of the starting materials, the polymers according to the invention and the comparative polymers

The molecular weights and molecular weight distributions were determined according to DIN 55672 part 1(2016-03) using Gel Permeation Chromatography (GPC). Tetrahydrofuran (THF) was used as eluent. Calibration was achieved using narrow distribution linear polyethylene glycol standards with molecular weights between 44,000 and 238 g/mol. The temperature of the column system was 40 ℃.

Description of the raw materials used

List of abbreviations used

IPDI Isophorone diisocyanate

PEG polyethylene glycol

Polydispersity index of PDI

Mn number average molecular weight

Mw weight average molecular weight

Preparation of a Monoadduct of a diisocyanate and a Monool

The alcohol is reacted with the diisocyanate to form the mono-adduct according to the procedure described in EP 1188779. All the mono-adducts were prepared in two steps comprising synthesis and removal of excess diisocyanate by thin film evaporation.

The IPDI and benzoyl chloride were heated to 40 ℃ and the alcohol was added dropwise. The reaction mixture was heated to 60 ℃ and stirred for 3 hours. The reaction conversion was controlled by measuring the isocyanate value.

Thereafter, the distillation of the excess IPDI is carried out at a temperature of from 100 ℃ to 150 ℃ by means of a thin-film evaporator. After this step, the monoadduct contains less than 0.2% by weight of residual diisocyanate.

TABLE 1 overview of the Monoadducts

Mono adduct no.	Alcohol(s)	Isocyanates
			MA-1	1-octanol	IPDI

Preparation of the polymers according to the invention and of the comparative polymers

Examples according to the invention urethane UR-1

In a four-necked round-bottomed flask equipped with a stirrer, reflux condenser and nitrogen inlet, 181.30 g (22.9 mmol) of Polyglykol 8000 were heated to 90 ℃. 0.10 g of bismuth carboxylate catalyst was added and, after homogenization, 18.7 g (45.9 mmol) of MA-1 were added. The reaction mixture was allowed to react at 90 ℃ for 3 hours. The reaction product was a highly viscous white product.

Comparative example CE-1

185.00 g (22.3 mmol) of Polyglykol 8000 were heated to 90 ℃ in a four-necked round-bottomed flask equipped with stirrer, reflux condenser and nitrogen inlet. 5.79 g (44.5 mmol) of 1-octanol and 0.10 g of bismuth carboxylate catalyst were added. After homogenizing the mixture, 9.89 g (44.5 mmol) of IPDI were added and the reaction mixture was reacted at 90 ℃ for 3 hours. The reaction product was a highly viscous white product.

TABLE 2 overview of the polymers prepared

Preparation of additive composition

The polyurethanes UR-1 and CE-1 were dissolved in the following formulation to form an aqueous additive composition.

TABLE 3 additive composition

TABLE 4 base (binder) for application testing (application testing)

Incorporation of additive composition:

the additive composition was post-added with stirring and thoroughly combined for 5 minutes using Dispermat LC3(VMA Getzmann GmbH; Reichhof, Germany).

Measurement of rheological properties in the base stock:

the reported values of shear viscosity of the base stocks were measured with a Rheometer Physica MCR 301(Anton Paar GmbH; Graz, Austria; CSR measurement, cone 2.5cm,1 °, shear rate 0.1-100001/s, 23 ℃).

TABLE 5 viscosity number [ Pas ] measured in base AC 2025 (active substance dosage: 0.1 wt-%)

TABLE 6 viscosity values [ Pas ] measured in the base Acronal S760 (active substance dosage: 0.2 wt-%)

TABLE 7 viscosity number [ Pas ] measured in base Uradil AZ554 (active substance dose: 0.2 wt-%)

And (4) conclusion:

the polymer UR-1 of the invention has been compared in various binders with the polymer prepared in random polymerization as described for comparative example CE-1. As can be seen in tables 5, 6 and 7, the polymers of the invention are superior to the comparative examples not of the invention in the increase in viscosity at the shear rate examined. Thus, polymer UR-1 of the present invention is a more efficient thickener than CE-1 resulting in increased shear viscosity.

Claims

1. A polymer comprising structural units according to formula (I),

R ¹-X-(C＝O)-NH-R ²-NH-(C＝O)-O-POA-R ³-(O-POA-R ⁴) _n

wherein

R ¹Represents an organic group terminated with a hydrocarbon group having 6 to 50 carbon atoms,

x represents O or N-R ⁵Wherein R is ⁵Represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms,

R ²represents an aliphatic hydrocarbon group having 4 to 40 carbon atoms,

POA represents a polyoxyalkylene group

R ³Represents an organic group having 2 to 40 carbon atoms,

n is an integer of 1 to 6

R ⁴Is independently selected from

-(C＝O)-NH-R ²-NH-(C＝O)-X-R ¹、

-(C＝O)-NH-R ¹、

-R ⁶Wherein R is ⁶Represents a hydrogen atom or has 1 to 24 carbon atomsAn aliphatic or aromatic group of (a) or (b),

and wherein the polymer has an average of at least 1.8 end groups R per molecule ¹A number average molecular weight of 2000 to 100000 daltons, a polydispersity of 1.0 to 5.0, wherein the quotient of the polydispersity divided by (n +1) is less than 1.0,

with the proviso that the polymer is not a reaction product of a) a mono-adduct of isophorone diisocyanate and 1-dodecanol with b) a polyether based on glycerol and a mixture of ethylene oxide and propylene oxide having an OH value of 18mg KOH/g.

2. The polymer according to claim 1, wherein X is O.

3. The polymer according to claim 1 or 2, wherein at least one R ¹Represents a polyoxyalkylene group terminated with a hydrocarbon group having 6 to 50 carbon atoms.

4. The polymer according to claim 1 or 2, wherein at least one R ¹Represents a hydrocarbon group having 6 to 30 carbon atoms.

5. A polymer according to any preceding claim, wherein the polyoxyalkylene group comprises a radical selected from- [ C ₂H ₄-O]-and- [ C ₃H ₆-O]-a repeating unit of (a).

6. The polymer according to any of the preceding claims, having a content of structural units according to formula (I) of at least 70 wt. -%, based on the total mass of the polymer.

7. A process for preparing a polymer according to any preceding claim, comprising reacting a compound of formula R ¹-X-(C＝O)-NH-R ²Compounds of formula-NCO (II) and HO-POA-R ³-(O-POA-R ⁴) _n(III) compound of (III) wherein R ¹To R ⁴POA, X and n are as defined above.

8. According to claimThe process of claim 7, wherein the reaction is carried out by reacting a compound of the formula OCN-R ²Diisocyanates of the formula-NCO (IV) & formula R ¹Reaction of a compound of formula XH (V) to obtain a compound of formula (II).

9. The process according to claim 8, wherein the reactivity of the isocyanate groups of the diisocyanates of the formula (IV) with the compounds of the formula (V) is different.

10. Use of a polymer according to any of the preceding claims 1 to 6 as a thickener in aqueous liquid compositions.

11. A composition comprising

a) The continuous aqueous liquid phase is a continuous aqueous liquid phase,

b) a polymer according to any of the preceding claims 1 to 6 dissolved in a continuous aqueous liquid phase, and

c) a hydrophobic component dispersed in the continuous aqueous liquid phase.

12. A composition according to claim 11, wherein the hydrophobic component is an organic film-forming binder.

13. The composition according to claim 11 or 12, further comprising solid particles.

14. The composition according to claim 13, wherein the solid particles are selected from the group consisting of pigments, fillers, and combinations thereof.

15. An additive composition comprising

a)10.0 to 60.0% by weight of a polymer according to any of the preceding claims 1 to 6,

b)40.0 to 90.0 wt.% of water,

c)0.0 to 1.0% by weight of a biocide, and

d)0.0 to 75.0 wt% of a viscosity inhibitor.